Nitridosilicates and oxonitridosilicates: from ceramic materials to structural and functional diversity

Silicates are one of the most important classes of compounds on this planet, and more than 1000 silicates have been identified in the mineral kingdom. Additionally, several hundreds of artificial silicates have been synthesized. The substitution of oxygen by nitrogen leads to the structurally diverse and manifold class of nitridosilicates. Silicon nitride, one of the most important non-oxidic ceramic materials, is the binary parent compound of nitridosilicates, and it symbolizes the inherent material properties of these refractory compounds. However, prior to the last decades, a broad systematic investigation of nitridosilicates had not been accomplished. In the meantime, these and related compounds have reached a remarkable level of industrial application. This review illustrates recent progress in synthesis and structure-property relationships and also applications of nitridosilicates, oxonitridosilicates, and related SiAlONs.     

New Insights into Keggin‐Type 12‐Tungstophosphoric Acid from 31P MAS NMR Analysis of Absorbed Trimethylphosphine Oxide and DFT Calculations

The acid and transport properties of the anhydrous Keggin‐type 12‐tungstophosphoric acid (H₃PW₁₂O₄₀; HPW) have been studied by solid‐state ³¹P magic‐angle spinning NMR of absorbed trimethylphosphine oxide (TMPO) in conjunction with DFT calculations. Accordingly, ³¹P NMR resonances arising from various protonated complexes, such as TMPOH⁺ and (TMPO)₂H⁺ adducts, could be unambiguously identified. It was found that thermal pretreatment of the sample at elevated temperatures (≥423 K) is a prerequisite for ensuring complete penetration of the TMPO guest probe molecule into HPW particles. Transport of the TMPO absorbate into the matrix of the HPW adsorbent was found to invoke a desorption/absorption process associated with the (TMPO)₂H⁺ adducts. Consequently, three types of protonic acid sites with distinct superacid strengths, which correspond to ³¹P chemical shifts of 92.1, 89.4, and 87.7 ppm, were observed for HPW samples loaded with less than three molecules of TMPO per Keggin unit. Together with detailed DFT calculations, these results support the scenario that the TMPOH⁺ complexes are associated with protons located at three different terminal oxygen (O_d) sites of the PW₁₂O₄₀³⁻ polyanions. Upon increasing the TMPO loading to >3.0 molecules per Keggin unit, abrupt decreases in acid strength and the corresponding structural variations were attributed to the change in secondary structure of the pseudoliquid phase of HPW in the presence of excessive guest absorbate.     

THREE-DIMENSIONAL THERMOELASTIC ANALYSIS OF FUNCTIONALLY GRADED PLATE

Three-dimensional thermoelastic analysis is presented for an orthotropic functionally graded rectangular plate,which is simply supported and isothermal on its four lateral edges.With the assumption that material properties have arbitrary dependence on the thickness-coordinate,a Peano-Baker series solution is obtained for the thermoelastic fields of the functionally graded plate subjected to mechanical and thermal loads on its upper and lower surfaces by means of state space method.The correctness of the obtained series solution is validated through numerical examples.The influence of different material properties distributions on the structural response of the plate is also studied.